Guanidine carbonate dispersion composition

ABSTRACT

A stable dispersion of guanidine carbonate and an ashless dispersing agent in mineral oil, the guanidine carbonate having a particle size in the range of 0.001 to 0.1 micron and being present at between about 1 to 50% by weight, the dispersing agent being present at between about 1 to 25% by weight; and a lubricant or hydrocarbon fuel composition containing an effective rust-inhibiting amount of the described mineral oil dispersion.

United States atent 11 1 1111 3,923,668 Johnston 1 1 Dec. 2, 1975 [54]GUANIDINE CARBONATE DISPERSION 2,737,496 3/1956 Catlin 252/5l.5 ACOMPOSITION 3,018,250 1/1962 Anderson ct al. 252/5l.5 A 3,172,892 3/1965Le Suer et al. 260/3265 5] Inventor: Thomas Emmett J n, West 3,275,5549/1966 Wagenaar 252 50 Gmve' OTHER PUBLICATIONS 1731 Assigneei deNemours and Chemical Abstracts, Vol. 79, 1973, 7075t.

Company, Wilmington, Del.

22 Filed; June 2 9 Primary ExaminerDelbert E. Gantz Assistant Examinerl.Vaughn [21] Appl- 482,571 Attorney, Agent, or Firm-James A. Costello 521U.S. (:1. 252/16; 44/51; 44/71; 1 1 ABSTRACT 252/34; 25 2/34.7; 252/50;252/51.5 A; A stable dispersion of guanidine carbonate and an ash-252/387; 252/392 less dispersing agent in mineral oil, the guanidinecar- [51] Int. Cl... C10M 1/32; ClOM 3/26; ClOL 1/32; bonate having aparticle size in the range of 0.001 to ClOL 1/22 0.1 micron and beingpresent at between about 1 to [58] Field of Search 44/51, 71; 252/16,34, 50% by weight, the dispersing agent being present at 252/34.7, 50,51.5 A, 387, 392 between about 1 to 25% by weight; and a lubricant orhydrocarbon fuel composition containing an effective [56] ReferencesCited rust-inhibiting amount of the described mineral oil dis- UNITEDSTATES PATENTS p 2,737,452 9 Claims, N0 Drawings 3/1956 Catlin et a1.44/62 GUANIDINE CARBONATE DISPERSION COMPOSITION BACKGROUND OF THEINVENTION 1. Field of the Invention This invention concerns guanidinecarbonate stably dispersed with an ashless dispersing agent in mineraloil. The invention also concerns lubricant and hydrocarbon fuelcompositions containing an effective rustinhibiting amount of theguanidine carbonate/dispersing agent/mineral oil composition.

2. Description of the Prior Art Lubricants and fuels are usually incontact with ferrous metals during storage and use. Since moisture andair are unavoidably present, corrosion of the ferrous metals will occur.In many cases, rusting and corrosion conditions are created because ofthe intrusion of products of combustion and/or oxidation during use ofthe lubricants and fuels. Thus, in the operation of an internalcombustion engine, engine blowby finds its way.into the crankcase.Depending upon the fuel used, blowby can contribute corrosive acids tothe crankcase.

The most practical method of controlling rust and corrosion by acids isto neutralize them. Thus, automotive crankcase lubricants generallycontain metal-based neutralizing additives to minimize the harmfuleffects of the acids. In many applications, however, the presence ofmetal compounds in lubricants and hydrocarbon fuels is undesirable. Oneobjection is that the lubricants and fuels show an increasedsusceptibility to oxidation which necessitates the use of higher levelsof antioxidants. Another objection is that metal compounds lead tometal-containing deposits, which are undesirable. In internal combustionengines, the formation of such deposits interferes with efficientoperation. In fuel oil burners, the accumulation of metalcontainingdeposits on the various parts eventually result in poorer burneroperation.

Metal-free rust inhibitors are known such as those based on long chainaliphatic amines, low molecular weight alkenylsuccinic acids,alkylthioacetic acids and substituted imidazolines. These metal-freerust inhibitors have not been entirely satisfactory because of limitedeffectiveness in the presence of acids. A need therefore exists for aneffective, ashless, rust inhibitor for lubricants and hydrocarbon fuelsthat is useful in acidic environments. The novel compositions of thisinvention fulfill this need.

Guanidine carbonate, although known in the art, is not known to be arust inhibitor. Nor is guanidine carbonate known in combination withmineral oil or dispersing agent. The present invention is based on thediscovery that stable dispersions of guanidine carbonate in mineral oilsusing certain ashless dispersing agents provide effective antirustprotection for lubricants and hydrocarbon fuels.

SUMMARY OF THE INVENTION This invention concerns a stable dispersion ofguanidine carbonate and ashless dispersing agent in mineral oilcomprising, based on percent by total weight,

i. from I to 50% guanidine carbonate having a particle size in the rangeof from 0.001 to 0.1 micron,

ii. from 1 to 25% of at least one oil-soluble, ashless dispersing agentselected from the group consisting of a. an aliphatichydrocarbylsuccinic acid and derivatives thereof wherein the hydrocarbylgroup has 30 to 200 carbon atoms, said derivative being selected fromthe group consisting of anhydride, ester, amide and aminoimide,

b. an aliphatic hydrocarbyl-substituted polyalkylene polyamine of theformula wherein R is selected from the group consisting of hydrogen,lower alkyl, and aliphatic hydrocarbyl containing from 30 to 200 carbonatoms, at least one R being said hydrocarbyl group, R is an alkyleneradical having 2 to 3 carbon atoms and x is 0 to 5, and

c. a basic amino nitrogen-containing addition type copolymer containingin copolymerized form at least one polymerizable ethylenicallyunsaturated monomer, free of amino-nitrogen and containing an aliphatichydrocarbyl chain of from 8 to 18 carbon atoms, and at least onepolymerizable ethylenically unsaturated monomer containing basic aminonitrogen, said copolymer containing 0.1 to 3.0% by weight of said basicamino nitrogen, said copolymer having an inherent viscosity of 0.1 to3.0 as determined at 0.1% weight volume concentration in benzene at25C., and

iii. from 25 to 98% of mineral oil having a 100F. viscosity of from 30to 1,500 SUS.

A preferred mineral oil dispersion contains from 10 to 42% of guanidinecarbonate, from 5 to 25% of the dispersing agent and from 33 to 85% ofthe mineral oil, based on total weight. Preferred dispersing agents arethe amino nitrogen-containing derivatives of hydrocarbylsuccinic acid.

The preferred ashless dispersing agents are characterized by thepresence of one or more amino groups,

which can be primary, secondary or tertiary amino groups. Thus, thepreferred dispersants of the hydrocarbylsuccinic class (a) are thoseprepared with a.

polyalkylene polyamine, so as to contain at least one amino nitrogen.The hydrocarbyl-substituted polyalkylene polyamines (b) and the aminonitrogen-containing copolymeric dispersing agents (0) inherently containone or more amino groups. These preferred dispersants are known in theart as additives for lubricating oils to disperse sludge and deposits.

The most preferred dispersing agent is the aminoimide derivative ofhydrocarbylsuccinic acid wherein the hydrocarbyl has from 50 to carbonatoms.

This invention also concerns compositions comprising a major proportionof a crankcase lubricant or fuel oil together with an effective rustinhibiting amount of the mineral oil dispersion. An effective amount ofthe mineral oil dispersion for inhibiting rust and corrosion willusually be such as to provide between about 0.5 to 5% of guanidinecarbonate based on the total weight of the composition. It should beappreciated, however, that amounts of the mineral oil dispersion thatprovide more than 0.1% of guandine carbonate and less than 0.5% willprovide some rust and corrosion-inhibiting properties, which propertieswill improve as the percentage of guanidine carbonate approaches themost effective range of 0.5 to 5%.

3 In this invention, by stable dispersion is meant one that shows littleor no settling of guanidine carbonate when stored at 25C. for one week.

DETAILS OF THE INVENTION Guanidine carbonate is a carbonic acid salt,2Cl-I N J-I CO of guanidine which is a strong base. Guanidine carbonatecan be prepared from guanidine and carbonic acid, but since guanidine isisolated only with difficulty, the carbonate is usually prepared byother known methods such as (l) heating dicyandiamide with ammoniumcarbonate or (2) heating cyanamide with ammonium carbonate.

Guanidine carbonate has a density of about 1.25 and melts at 241C. It issoluble in water (45 g per 100 g water at C. and is sparingly soluble innonpolar organic liquids such as benzene, toluene, hexane, petroleumoils, and the like. To be an effective anitrustant in lubricants andfuel oils, guanidine carbonate must be provided in a suitable form.Since guanidine carbonate itself is insufficiently soluble in lubricantsand hydrocarbon fuels to be effective, it is provided herein as a stabledispersion in mineral oil.

Stable dispersions of guanidine-carbonate in mineral oil are obtainedwhen the average particle size of guanidine carbonate is in the range of0.001 to 0.1 micron, and certain ashless dispersing agents are used.When the average particle size is greater than about 0.1 micron, thedispersions are turbid and the guanidine carbonate settles out morerapidly than is desired. Thus, a stable dispersion has an averageparticle size of about 0.1 micron or less. The preferred particle sizeis about 0.05 micron or less.

Numerous methods are known for making solid guanidine carbonate finelydivided. These methods include grinding and ball milling in liquid mediawith and without dispersing agents. These mechanical methods, however,are generally time consuming and costly. It has been found that stabledispersions of guanidine carbonate can be prepared by emulsifying anaqueous guanidine carbonate solution in a mineral oil in the presence ofa suitable dispersing agent and (2) removing the water by azeotropicdistillation at low temperature. By this process, guanidine carbonatestably dispersed in mineral oil and having an average particle size ofabout 0.05 micron is readily and economically prepared.

It is recognized that the stability of dispersions in general dependsupon the particle size and the nature of the solid, the nature of thesolid surface, the'properties of the liquid medium and thecharacteristics of the dispersing agent. Dispersing agents are generallysurface active agents characterized by having lipophilic and hydrophilicgroups. Dispersing agents useful in the present invention should beoil-soluble, that is soluble to the extent of at least 0.05 g. per 100g. of mineral oil. Oil-soluble dispersing agents generally contain atleast one oil-solubilizing group, usually an alkyl or an alkenyl groupof at least about 8 carbon atoms, more usually at least 12 carbon atoms.Since the dispersions of the invention will find applications in systemswhich are desirably ash-free or of very low ash, the dispersing agentsshould also be ash-free, that is, be substantially free of metalliccomponents.

Since the preferred method for preparing stable guanidine carbonatedispersions includes the preparation of an emulsion of aqueous guanidinecarbonate in mineral oil, it is desirable that the dispersing agent also4 be effective as an emulsifying agent in the above process. Thoseskilled in the art can easily determine the suitability of a surfaceactive compound as an emulsifying agent and as a dispersing agent by asimple experiment as described in Example 1.

Dispersing agents useful in the present invention in clude highmolecular weight hydrocarbylsuccinic acid and certain derivativesthereof. In the present context, the term hydrocarbyl includes alkyl andalkenyl groups. The hydrocarbylsuccinic acids are known in the art; Theyare prepared by the reaction of maleic anhydride with high molecularweight aliphatic olefins or with chlorinated high molecular weightaliphatic olefins to provide in each case a high molecular weightaliphatic hydrocarbylsuccinic anhydride. The high molecular weightolefin can be any olefin but is preferably a polymer of a C to C olefin,most preferably polypropylene or polyisobutylene. To provide oilsolubility to the hydrocarbylsuccinic acid the olefin should contain atleast 30 carbon atoms, preferably in the range of 50 to 200 carbonatoms. The hydrocarbylsuccinic anhydride obtained as described above canbe (a) hydrolyzed to the acid, (b) condensed with a hydroxyl-containingcompound such as sorbitol to provide either the monoor diester, or (c)reacted with a polyalkylene polyamine having at least one amino hydrogento provide derivatives which include corresponding substituted amidesand imides.

The preferred dispersing agent is the imide reaction product of ahydrocarbylsuccinic acid and a substantially equimolar amount of apolyalkylene polyamine having a free NI-I group and is represented bythe formula wherein R is an aliphatic hydrocarbyl group of 30 to 200carbon atoms, R is an alkylene group of 2 to 3 carbon atoms, R and R areselected from the group consisting of hydrogen and lower alkyl groupsand x is 0 to 5.

The particularly preferred dispersing agents are imides of the aboveformula wherein R is a hydrocarbyl group of 50 to carbon atoms, R is analkylene group of 2 carbon atoms, R and R are hydrogens and x is 4.Specific polyalkylene polyamines suitable for the preparation of suchimides include ethylenediamine,

diethylenetriamine, triethylenetetramine, tetraethylenepentamine,pentaethylenehexamine, hexaethyleneheptamine, 1,2-propylenediamine, 1,3-

propylenediamine, di- 1 ,2-propylenetriamine, tri-l ,2-propylenetetramine, di-l ,3-propylenetriamine, tri-l ,3-propylenetetramine, N,N-dimethylethylenecliamine,N,N-diethylpropylenediamine and the like. It is understood that whilethe above reaction product is described in terms of aminoimide, theproduct can also contain amides as well as amine carboxylates.

Another class of useful dispersing agents comprises certain highmolecular weight oil-soluble aliphatic hydrocarbyl substitutedpolyamines. This type of dispersing agent is usually prepared byhalogenation of a high molecular weight olefin such as polypropylene orpolyisobutylene, to form an alkyl or alkenyl halide which is then usedto alkylate a polyalkylene polyamine having a replaceable aminohydrogen.To provide sufficient oil solubility to the resulting hydrocarbylatedpolyalkylene polyamine, the olefin should contain at least about 30carbon atoms preferably 50 to 200 carbon atoms. Depending upon the molarproportions and the reaction conditions, the resulting alkylatedpolyalkylene polyamine contains one or more high molecular weighthydrocarbyl group(s). This type of dispersing agent is represented bythe formula wherein R is selected from the group consisting of hydrogen,lower alkyl, and aliphatic hydrocarbyl containing from 30 to 200 carbonatoms, at least one R being said hydrocarbyl group, R is an alkyleneradical having 2-3 carbon atoms and x is 0 to 5. Usually only one of theR groups is hydrocarbyl. Polyalkylene polyarnines suitable for thepreparation of such hydrocarbyl derivatives include ethylenediamine,diethylenetriamine, triethylenetetramine, tetraethylenepentamine,pentaethylenehexamine, hexaethyleneheptamine, 1,2- and1,3-propylenediamine, di-l,2- and 1,3-propylenetriamine, tri-l,2-propylenetetramine, N-methylethylenediamine,N-methyl-1,3-propylenediamine, N,N- dimethylethylenediamine,N,N-dimethyl-l ,3- propylenediamine and the like.

Another useful class of ashless dispersing agent for the preparation ofthe novel compositions comprises basic nitrogen-containing addition typecopolymers containing in copolymerized form at least one ethylenicallyunsaturated polymerizable monomer, free of amino nitrogen and containingan aliphatic hydrocarbyl chain of from 8 to 18 carbon atoms, and atleast one ethylenically unsaturated polymerizable monomer containingbasic amino nitrogen, the copolymer containing 0.1 to 3.0% by weight ofthe basic amino nitrogen and having an inherent viscosity of 0.1 to 3.0as determined at 0.1% weight-volume concentration in benzene at 25C.

Useful polymers include copolymers of lauryl methacrylate anddiethylaminoethyl methacrylate, n-octyl methacrylate anddiethylaminoethyl methacrylate, tridecyl methacrylate anddimethylaminoethyl methacrylate, octadecyl methacrylate anddimethylaminoethyl methacrylate, lauryl methacrylate andp-dimethylaminomethylstyrene and the like. The preferred copolymercontains 90% by weight of lauryl methacrylate and 10% by weight ofdiethylaminoethyl methacrylate.

The mineral oil of the composition is characterized by having a 100F.viscosity in the range of 30 to 1500 SUS. The choice of the particularmineral oil depends partially on the intended use of the composition.When the composition is to be added to a lubricating oil such ascrankcase oil, the mineral oil will preferably have its 100F. SUSviscosity in the range 50 to 600. When the composition is to be added toa hydrocarbon fuel oil, the mineral oil will preferably have a 100F.viscosity in the range 30 to 60.

The substrates to which the composition of the invention can be added toprovide antirust protection include lubricants and hydrocarbon fuels.Lubricants include greases, crankcase lubricants for internal combustionengines, turbine oils. hydraulic oils, gear oils and slushing oils,derived either from mineral oil or 6 from various synthetic sources suchas polymerized olefins and ester-type compositions.

The mineral oil-lubricant composition which has a major proportion ofmineral oil of lubricating viscosity can also contain conventionaladditives such as viscosity index improvers, dispersants, pour pointdepressants, antioxidants, corrosion inhibitors, antiwear agents, rustinhibitors, antifoam agents, metal deactivators and the like.Hydrocarbon fuels include kerosene, diesel fuel, home heating oil andresidual fuel. Hydrocarbon fuels can also contain additives commonlyused therein such as dispersants, antioxidants, antirust agents,antiwear agents, and the like.

The compositions of the invention, particularly those havingamino-containing ashless dispersants, are unexpectedly effective toinhibit rusting of ferrous metals in severely corroding acidenvironments. Such an environment exists, for example, in an automotiveengine crankcase where water, hydrochloric acid, hydrobromic acid,sulfuric acid and organic acids are introduced in the blowby. Theseacids are formed in the combustion process from ethylene chloride, andethylene dibromide, sulfur in the fuel, and incomplete combustion of thefuel components. Exposed to such conditions, ferrous metals rapidlycorrode and rust. Neither guanidine carbonate alone nor theamine-containing dispersant alone provides adequate protection. It issurprising, therefore, that the combination does provide such goodprotection.

A particularly useful combination is that of the invention compositionswith ashless amino nitrogen-containing sludge and deposit dispersantsfor lubricating oils. Such combination provides enhanced rustprotection. Since certain of these ashless amino nitrogen-containingdispersant additives for lubricating oils are also the preferreddispersants for the present composition, the desirable combination canbe made by incorporating additional amounts of such dispersants in thepresent compositions or by adding the present composition to lubricantsalready containing such dispersants.

The following Examples are meant to illustrate the invention.

EXAMPLE 1 Polyisobutenylsuccinic anhydride (30 g) (polyisobutenylformula weight=l ,400) was dissolved in a mixture of g. of mineral oilof SUS viscosity at 100F. and 50 ml. of toluene. The oil solution wasadded to an homogenizer of 1 liter capacity, and, with the blenderoperating at the medium speed, g. of a 25% aqueous solution of guanidinecarbonate was added over a period of 2 to 3 minutes. The blender wasthen operated at high speed for 8 to 10 minutes to produce a stableemulsion. The emulsion was transferred to a distillation flask equippedwith an agitator, a thermometer and a Dean-Stark water separator. Thecontents of the flask was heated to 50-60C. at 550 to 600 mm pressure toremove water azeotropically. After all of the water had been removed,toluene was removed at 70C. and 700 mm pressure.

The product remaining was a dark amber liquid composition containing 25%by weight of dispersed guanidine carbonate, 19% by weight of thedispersing agent and 56% by weight of the mineral oil. The dispersionstored at room temperature for one week showed no sign of separation ofguanidine carbonate. Electron microscopic examination of the dispersionshowed that the average size of the guanidine carbonate particles was inthe range 0.05 to 0.1 micron.

EXAMPLES 2 to 10 Using the procedure as described in Example 1 and theappropriate amounts of the guanidine carbonate 5 known ReferenceSequence IIC Test Method. In this solution and the mineral oil used inExample 1, stable test a carefully cleaned and assembled engine isoperguanidine carbonate dispersions were prepared as ated on adynamometer test stand for a total of 32 listed below. Particularlynotable is the composition of hours under controlled conditions ofengine speed, Example 7 which provided a very clear dispersion. coolanttemperature, and air-fuel ratio. At the comple- TABLE DispersingGuanidine Dispersing Mineral Example Agent Carbonate Agent Oil No. UsedWt.% Wt.% Wt.%

2 of Example 1 20 1O 70 3 of Example 1 l 85 4 of Example 1 42 l7 4] 5Polypropenylsuccinic l0 5 85 anhydride" 6 Polyisobutenylsuccinic l0 5 8Sacid-sorbit0l ester 7 Polyisobutenylsuccinimide 55 8Polyisobutenylsuccimimide l9 9 72 9 Polyisobutenylsuccinimide 50 25 25lo Polyisobutenyltetraethylene pentamine 20 1O 70 ll LM/DEAM Copolymer20 10 70 "'Formula weight (FW) of polypropenyl group 800 'Diester. FW ofpulyisohutenyl group 1400 Monoimide of tetraethylene pentamine, FW ofpolyisobutenyl group 1400 FW of polyisobutenyl group I200 *Copolymer of90% (by weight) lauryl methacrylate and l0% (by weight)ofdiethylaminoethyl methacrylate.

EXAMPLE 12 The antirust properties of the invention composition in fueloil were determined according to the modified method of ASTM D665,Procedure A, employing the composition of Example 7.

In this test, 300 ml. of No. 2 fuel oil containing the additive undertest was stirred with ml of distilled water at a temperature of 32C.(90F.) with a cylindrical steel specimen completely immersed therein.The test was carried out for 20 hours. At the conclusion of the test,the condition of the steel specimen was rated as rust-free, lightrusting, moderate rusting or severe rusting. The results summarizedbelow show that the novel composition when added to fuel oil in suchamount to produce a total weight percent of guanidine carbonate of 0.5%was effective in preventing the rusting of steel.

Additive (Wt.%) Steel Specimen Moderate rusting Moderate rustingRust-free None (Control Fuel Oil) 0.1%

EXAMPLE 13 tion of the test, the engine is disassembled and five parts,namely, lifter bodies, plungers, balls, relief valve plungers and pushrods are each rated for rusting and corrosion by reference to a standardcolor chart wherein 10 is a perfect rating. The average value of theratings of the parts characterizes the performance of the lubricatingoil. The test results indicated that the composition of this inventionimproved the rusting and corrosion characteristics of lubricating oilsince a rating of 7.3 was achieved by an oil blend containing thecomposition of this invention whereas a rating of only 4.7 was achievedemploying a conventional ashless antirustant.

EXAMPLE 14 The utility of a composition of the present invention toprotect ferrous metals under severe corrosion and rusting conditions wasdemonstrated in the following test. A 1020 mild steel billet, A X 56 X6, inches, is placed in a 4 oz. glass bottle, and 30 ml of test oilblend is added to the bottle making sure that the entire billet iscoated with the test oil. To the bottle, 3 ml of an aqueous acidsolution containing 0.97 wt. each of hydrochloric acid, hydrobromicacid, sulfuric acid, nitric acid and acetic acid as well as 0.02 wt. oflead chloride and lead bromide is added. The bottle is closed, placed inan oven at 5F., then alternately rotated and allowed to stand for 4-hourperiods for a total of 24 hours. At the conclusion of the test, thebillet is removed from the bottle, rinsed free of oil and visuallyexamined for rust and corrosion.

Three oil blends were prepared, each having a total base number (TBN) of9.5. Total base number is determined by ASTM D2896 Method wherein theoil blend is titrated with perchloric acid in glacial acetic acid and isdefined as the quantity of perchloric acid expressed in terms ofequivalent number of milligrams of potas- 9 sium hydroxide required toneutralize all basic constituents in 1 g of sample (ASTM D2896, 1973).

Blend A contained 9.22% by weight of the guanidine carbonate dispersionof Example 2(l.84 wt. guanidine carbonate) TBN=9.5.

Blend B contained 1 1.5 wt. ofa polyisobutenylsuccinimide derived fromtetraethylenepentamine. (Formula weight of polyisobutenyl group 1,400)TBN 9.5.

Blend C contained 1.12 wt. of the guanidine carbonate used in Blend Aand 4.5 wt. of the polyisobutenylsuccinimide used in Blend B, TBN 9.5.

Each of the blends A, B, and C was tested as described above andcompared with the control oil (no additive). The results are summarizedbelow.

The results demonstrate that Blend C, a combination of guanidinecarbonate and an amine-containing dispersing agent, provides unexpectedprotection for ferrous metal in a severely corroding and rusting acidenvironment. Blend A is also somewhat effective in protecting the steelbillet although not to the extent of Blend C.

The embodiments of the invention in which an exclusive property orprivilege is claimed are defined as follows:

l. A stable dispersion of guanidine carbonate and ashless dispersingagent in mineral oil comprising, based on percent by total weight,

i. from 1% to 50% of guanidine carbonate having a particle size in therange of from 0.001 to 0.1 micron, ii. from 1% to 25% of at least oneoil-soluble, ashless dispersing agent selected from the group consistingof a. an aliphatic hydrocarbylsuccinic acid and derivatives thereofwherein the hydrocarbyl group has 30 to 200 carbon atoms, saidderivative being selected from the group consisting of anhydride, ester,amide and aminoimide,

b. an aliphatic hydrocarbyl-substituted polyalkyle ne polyamine of theformula wherein R is selected from the group consisting of hydrogen,lower alkyl, and aliphatic hydrocarbyl containing from 30 to 200 carbonatoms, at least one R being said hydrocarbyl group, R is an alkyleneradical having 2 to 3 carbon atoms and x is 0 to 5, and

c. a basic amino nitrogen-containing addition type copolymer containingin copolymerized form at least one polymerizable ethylenicallyunsaturated monomer, free of amino-nitrogen and containing an aliphatichydrocarbyl chain of from 8 to 18 carbon atoms, and at least onepolymerizable ethylenically unsaturated monomer containing basic aminonitrogen, said copolymer containing 01 to 3.0% by weight of said basicamino nitrogen, said copolymer having an inherent viscosity of 0.1 to3.0 as determined at 0.1% weight volume concentration in benzene at25C., and

iii. from 25% to 98% of mineral oil having a 100F.

viscosity of from 30 to 1,500 SUS.

2. A stable dispersion according to claim 1 containing from 10 to 42%guanidine carbonate 5 to 25% dispersing agent, and

33 to 85% mineral oil.

3. A stable dispersion according to claim 1 wherein the dispersing agentcontains at least one amino group.

4. A stable dispersion according to claim 3 wherein the dispersing agentis aminoimide of hydrocarbylsuccinic acid wherein the hydrocarbyl grouphas from 50 to carbon atoms.

5. A stable dispersion according to claim 3 wherein the dispersing agentis polyisobutenylsuccinimide.

6. A stable dispersion according to claim 3 wherein the dispersing agentis polyisobutenyltetraethylene pentamine.

7. A stable dispersion according to claim 3 wherein the dispersing agentis lauryl methacrylate/diethylaminoethyl methacrylate copolymer.

8. A crankcase lubricating composition comprising mineral oil oflubricating viscosity and an effective amount of the stable dispersionof claim 1 providing from about 0.5 to 5%, by total weight, of guanidinecarbonate.

9. A fuel oil composition comprising hydrocarbon fuel oil and aneffective amount of the stable dispersion of claim 1 providing fromabout 0.5 to 5%, by total weight, of guanidine carbonate.

1. A STABLE DISPERSION OF GUANIDINE CARBONATE AND ASHLESS DISPERSINGAGENT IN MINERAL OIL COMPRISING, BASED ON PERCENT BY TOTAL WEIGHT, I.FROM 1% TO 50% OF GUANIDINE CARBONATE HAVING A PARTICLE SIZE IN THERANGE OF FROM 0.001 TO 0.1 MICRON, II. FROM 1% TO 25% OF AT LEAST ONEOIL-SOLUBLE, ASHLESS DISPERSING AGENT SELECTED FROM THE GROUP CONSISTINGOF A. AN ALIPHATIC HYDROCARBYLSUCCINIC ACID AND DERIVATIVES THEREOFWHEREIN THE HYDROCARBYL GROUP HAS 30 TO 200 CARBON ATOMS, SAIDDERIVATIVE BEING SELECTED FROM THE GROUP CONSISTING OF ANHYDRIDE, ESTER,AMIDE AND AMINOIMIDE, B. AN ALIPHATE HYDROCARBYL-SUBSTITUTEDPOLYALKYLENE POLYAMINE OF THE FORMULA
 2. A stable dispersion accordingto claim 1 containing from 10 to 42% guanidine carbonate 5 to 25%dispersing agent, and 33 to 85% mineral oil.
 3. A stable dispersionaccording to claim 1 wherein the dispersing agent contains at least oneamino group.
 4. A stable dispersion according to claim 3 wherein thedispersing agent is aminoimide of hydrocarbylsuccinic acid wherein thehydrocarbyl group has from 50 to 150 carbon atoms.
 5. A stabledispersion according to claim 3 wherein the dispersing agent ispolyisobutenylsuccinimide.
 6. A stable dispersion according to claim 3wherein the dispersing agent is polyisobutenyltetraethylene pentamine.7. A stable dispersion according to claim 3 wherein the dispersing agentis lauryl methacrylate/diethylaminoethyl methacrylate copolymer.
 8. Acrankcase lubricating composition comprising mineral oil of lubricatingviscosity and an effective amount of the stable dispersion of claim 1providing fRom about 0.5 to 5%, by total weight, of guanidine carbonate.9. A fuel oil composition comprising hydrocarbon fuel oil and aneffective amount of the stable dispersion of claim 1 providing fromabout 0.5 to 5%, by total weight, of guanidine carbonate.